TiCl4-Cr还原偶联活泼卤化物及芳醛、芳酮的研究

低价钛化合物在有机合成和有机反应中有着广泛的应用。我们曾研究了低价钛对α,α,α-三卤甲基苯的脱卤偶联、对2,2-二芳     

The Weak Interaction on CO2 …CO van der Waals Complex : A Theoretical Study

The geometries of van der Waals complex CO2…CO were optimized at DFT and second-order Moller-Plesset perturbation(MP2) levels with the large basis set,three stable structures were found.The most stable structure has a T-shape geometry in which the CO lies along the C2 axis of CO2,with the two C atoms direct contact and R(C…C)=0.3227nm.The corresponding energies of the most stable structure were calculated by means of MP2,MP4D,MP4DQ,MP4SDTQ,MP4SDQ,CCSD and CCSD(T) methods,The BSSE (basis set superposition error) wads eliminated by the Boys-Bernardi counterpoise correction(CP) method.According to thermodynamics data.van der Waals complex CO2…CO can found at a low temperature and or a high pressure,There is a little charge transferred between the two interacted subunits.In the most stable structure,CO2 is the acceptor and CO is the donor.     

双二氮杂萘酮类化合物的电喷雾质谱研究

含新型芳香杂环单元的缩聚高分子材料耐老化热稳定性好,具有独特的加工长度和弹性模量,在宇航、电子、机械、军事和复合材料等方面的应用已引起人们的广泛兴趣和关注。含双二氮杂萘酮单元的缩聚高分子材料就是其中一种,这些新型芳香杂环单元大多数熔点都较高,难于汽化,采用电子轰击质谱或快原子轰击质谱测定其相对分子质量时,通常得不到分子离子峰信号,给质谱表征和结构鉴定带来一定的困难。     

热致液晶聚合物分散相的形态及其与树脂连续相之间的相互作用

用动态力学谱仪和扫描电子显微镜测试观察了六个含热致液晶聚合物（ＴＬＣＰ）共混体系中的相间相互作用与微结构．组份损耗峰向内或大或小的移动表明在这些共混物中存在着强弱不同的相间相互作用．在各个共混物中所含ＴＬＣＰ公相的形态有圆球状、椭球状、条状和微纤状的．结果表明，在含ＴＬＣＰ的不相容聚合物共混体系中，相间相互作用与微纤形成之间没有直接的相关性．     

一维链状配位聚合物{[Cu(μ-H_2L)(L)Cl](ClO_4)_3}_∞的合成、结构及磁性研究(L=N,N'-双(吡啶基-3-亚甲基)-1,5-二氮环辛烷)

设计合成了一个新型吡啶基二氮环配体L(N,N'-双(吡啶基-3-亚甲基)-1,5-二氮环辛烷)及其铜配位聚合物{[Cu(滋-H2L)(L)Cl](ClO4)3}∞(1),研究了此配合物的晶体结构、光谱及磁性质。该配合物属正交晶系,Pnma空间群,晶胞参数为a=3.5170(17)nm,b=1.0440(5)nm,c=1.1966(6)nm,V=4.394(4)nm3,Z=4。配体L以顺式螯合和反式桥联两种不同的配位形式将铜离子连接起来形成一维链状阳离子结构。     

Coupling matrix element of electron self-exchange reactions in solution

On the basis of the common feature among the electron transfer process and the ion hydration process as well as the relevant experimental kinetic data of electron transfer reaction,a new accurate hydration potential function scheme for the determination of electron transfer coupling matrix element is presented.The coupling matrix element between two hydrated ions of the reacting system in solution is calculated.The results and the applicability of this scheme are discussed.     

新型有序结构分子聚集体的构筑

本文概述了近年来我们在新型有序结构分子聚集体构筑方面取得的一些主要成绩，并展望了今后进一步的研究和发展方向。     

CRYSTALLIZATION AND MELTING OF NYLON 610

Differential scanning calorimetry was used to study the crystallization andmelting of nylon 610. For nylon 610 crystallized from the melt state (260℃), the overall rateof bulk crystallization can be described by a simple Avrami equation with Avrami exponentn ≈ 2, independent of crystallization temperature. With the experimentally obtainedT_m~0 (235℃ ～ 255℃) of nylon 610, the fold surface free energy σ_e was determined to be35 ～38 erg/cm~2. The effects of annealing temperature and time on the melting of quenchednylon 610 were also investigated. For nylon 610 quenched at room temperature there isonly one DSC endotherm peak DSC scans on annealed samples exhibited an endothermpeak at approximately 10℃ above the annealing temperature. The size and position of theendothermic peak is strongly related to annealing temperature and time. An additionalthird melting was observed when quenched nylon 610 was annealed at high temperaturefor a sufficiently long residence time. The existence of the third melting peak suggests thatmore than one kind of distribution of lamella thickness may occur when quenched nylon610 is annealed. The implications of these results in terms of crystal thickening mechanismwere discussed.     

化学蒸气发生-电感耦合等离子体原子发射光谱法测定地质样品中痕量金

地质样品经盐酸-硝酸(3+1)混合酸溶解,活性炭分离富集后,于90℃用12g.L-1硼氢化钠溶液(溶于0.5g.L-1氢氧化钠溶液中)作还原剂,用化学蒸气发生-电感耦合等离子体原子发射光谱法测定其中痕量的金。金的质量浓度在1 500μg.L-1以内与其发射强度呈线性关系,方法的检出限(3s)为0.59μg.L-1。方法用于测定2个标准物质(GBW 07289和GBW 07291)中金含量,测定值与认定值相符。     

可注射型酶促高分子水凝胶的制备及表征

利用聚乙二醇（PEG，相对分子质量2 000）与对羟基苯丙酸（DAT）的酯化反应得到凝胶因子，在辣根过氧化物酶（HRP）和过氧化氢催化体系的作用下，制备了一种新型的能快速固化的可注射型水凝胶。研究了HRP、凝胶因子和过氧化氢浓度对凝胶时间的影响，结果表明，当凝胶因子浓度高、HRP浓度高、过氧化氢浓度较低时，凝胶时间较短，最短可在3 s内凝胶。采用红外光谱和核磁共振氢谱对凝胶因子的结构进行了表征，并提出了HRP/H2O2酶促催化下凝胶因子的自由基聚合机理。